US2889272A - Catalytic desulfurization of petroleum hydrocarbons in a two stage autofining process - Google Patents
Catalytic desulfurization of petroleum hydrocarbons in a two stage autofining process Download PDFInfo
- Publication number
- US2889272A US2889272A US572785A US57278556A US2889272A US 2889272 A US2889272 A US 2889272A US 572785 A US572785 A US 572785A US 57278556 A US57278556 A US 57278556A US 2889272 A US2889272 A US 2889272A
- Authority
- US
- United States
- Prior art keywords
- autofining
- distillate
- pressure
- conditions
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 14
- 238000006477 desulfuration reaction Methods 0.000 title claims description 9
- 230000023556 desulfurization Effects 0.000 title claims description 9
- 230000003197 catalytic effect Effects 0.000 title claims description 7
- 229930195733 hydrocarbon Natural products 0.000 title description 3
- 150000002430 hydrocarbons Chemical class 0.000 title description 3
- 239000003208 petroleum Substances 0.000 title description 3
- 239000003054 catalyst Substances 0.000 claims description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 239000003209 petroleum derivative Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- 238000009835 boiling Methods 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000012958 reprocessing Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
Definitions
- This invention relates to the catalytic dcsulfurization of petroleum hydrocarbons by means of the autofining process, the nature of which is described inter alia in United States Patents Nos. 2,573,726, 2,574,445-51 and 2,540,802.
- the autofining operation is carried out under a temperature selected between about 650-800 F. and a pressure selected between 25-500 p.s.i. ga. with the temperature and pressure being correlated with respect to one another to insure a net production of hydrogen.
- Plants suitable for the autofining of the lower boiling feedstocks may not necessarily be adapted for operation at the higher pressures reached when autofining under equilibrium pressure conditions, but it would nevertheless be desirable if the higher boiling petroleum distillates could be adequately desulfurized in such plants.
- a process for the catalytic desulfurization of a petroleum distillate comprises autofining the distillate at a pressure below the equilibrium pressure and recycling the treated distillate to the reaction zone, or reprocessing the treated distillate,
- the invent-ion is particularly applicable to the autofining of gas oils.
- the catalyst employed is preferably 'of the kind comprising the oxides of cobalt and molybdenum either as such or in combined form incorporated with a metal oxide support, usually alumina.
- the catalyst may with advantage comprise a small amount, preferably between 0.1% and 6.0% by weight, of fluorine as described in United States patent application Ser. No. 311,429, filed September 25, 1952, now US. :Patent No. 2,800,429. "The use of .such a catalyst does not increase the degree of :desulfurization unless equilibrium pressure operation is employed, but even .at lower pressures it has the effect of producing a greater net yield of hydrogen which may with advantage be used in other processes in the refinery.
- the invention will now -be described with reference to the followingexamples:
- Example 1 t A Kuwait gas oil was autofined in a pilot plant having a mlncatalyst capacity under the following conditions:
- the liquid product was washed with caustic soda solution and water to remove dissolved hydrogen sulfide and then reprocessed under the same conditions over a fresh charge of catalyst.
- Two types of catalyst were used, a catalyst consisting of the oxides of cobalt and molybdenum supported on alumina and a catalyst of similar composition but activated with aluminum fluoride.
- Example 2 The same feedstock as in Example 1 was processed under the same conditions as in Example 1, using the catalyst that. did not contain fluorine,for five-processing periods, at the end of which the sulfur content of the product had been reduced to 0.17% wt. The results obtained were as follows:
- dehydrogenation-hydrogenation catalyst is oxides of cobalt and molybdenum on alumina.
- a process for the catalytic desulfurization under autofining conditions of a petroleum distillate that cannot be adequately desulfurized under autofining conditions on a once-through basis at pressures below the equilibrium autofining pressure of the distillate obtainable under the autofining conditions of catalyst, temperature, and space velocity existingin the autofining zone which comprises contacting the distillate in a reaction zone with a dehydrogenation-hydrogenation catalyst and hydrogen derived solely from the distillate at a temperature between about 650800 F. and at a.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8272/55A GB792496A (en) | 1955-03-22 | 1955-03-22 | Improvements relating to the catalytic desulphurisation of petroleum hydrocarbons |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2889272A true US2889272A (en) | 1959-06-02 |
Family
ID=9849311
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US572785A Expired - Lifetime US2889272A (en) | 1955-03-22 | 1956-03-21 | Catalytic desulfurization of petroleum hydrocarbons in a two stage autofining process |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US2889272A (enrdf_load_stackoverflow) |
| BE (1) | BE546109A (enrdf_load_stackoverflow) |
| DE (1) | DE1074182B (enrdf_load_stackoverflow) |
| FR (1) | FR1144451A (enrdf_load_stackoverflow) |
| GB (1) | GB792496A (enrdf_load_stackoverflow) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6454934B2 (en) * | 1997-09-11 | 2002-09-24 | Jgc Corporation | Petroleum processing method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2604436A (en) * | 1950-01-17 | 1952-07-22 | Anglo Iranian Oil Co Ltd | Catalytic desulfurization of petroleum hydrocarbons |
| US2606141A (en) * | 1948-04-19 | 1952-08-05 | Anglo Iranian Oil Co Ltd | Catalytic desulfurization of petroleum hydrocarbons |
| US2718490A (en) * | 1952-05-21 | 1955-09-20 | British Petroleum Co | Catalytic desulphurisation of petroleum hydrocarbons |
-
0
- DE DENDAT1074182D patent/DE1074182B/de active Pending
- BE BE546109D patent/BE546109A/xx unknown
-
1955
- 1955-03-22 GB GB8272/55A patent/GB792496A/en not_active Expired
-
1956
- 1956-03-21 US US572785A patent/US2889272A/en not_active Expired - Lifetime
- 1956-03-21 FR FR1144451D patent/FR1144451A/fr not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2606141A (en) * | 1948-04-19 | 1952-08-05 | Anglo Iranian Oil Co Ltd | Catalytic desulfurization of petroleum hydrocarbons |
| US2604436A (en) * | 1950-01-17 | 1952-07-22 | Anglo Iranian Oil Co Ltd | Catalytic desulfurization of petroleum hydrocarbons |
| US2718490A (en) * | 1952-05-21 | 1955-09-20 | British Petroleum Co | Catalytic desulphurisation of petroleum hydrocarbons |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6454934B2 (en) * | 1997-09-11 | 2002-09-24 | Jgc Corporation | Petroleum processing method |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1144451A (fr) | 1957-10-14 |
| BE546109A (enrdf_load_stackoverflow) | |
| DE1074182B (de) | 1960-01-28 |
| GB792496A (en) | 1958-03-26 |
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